CA1199147A - Non-crystalline polyamine/carbonic acid salt compositions, a process for their preparation and their use for the production of polyurethane ureas, especially foamed coatings - Google Patents

Abstract

NON-CRYSTALLINE POLYAMINE/CARBONIC ACID
SALT COMPOSITIONS, A PROCESS FOR THEIR
PREPARATION AND THEIR USE FOR THE PRODUCTION
OF POLYURETHANE UREAS, ESPECIALLY FOAMED COATINGS
ABSTRACT OF THE DISCLOSURE
This invention relates to new liquid or fluid polyamine/carbonic acid salt compositions free from crystalline content and their preparation from mixtures containing at least one aliphatic or cycloaliphatic polyamine, an aliphatic or cycloaliphatic hydroxyamine having at least one hydroxyl group and at least one amino group, and water and optionally diluents and/or conventional auxiliary agents and additives, by the addition of carbon dioxide. The proportion of poly-amine to hydroxyamine is in the range of from about 95:5 to 10:90 % by weight, the quantity of water added is from about 0.01 to 5 mol of H2O per amine equiva-lent (but at least 1 mol of water per mol of CO2) and the quantity of CO2 added is from about 0.01 to 0.99 mol of CO2 per amine equivalent. The invention further relates to the use of these liquid polyamine/
carbonic acid salt compositions for the production of foamed polyurethane ureas, especially for coating substrates or for the production of sheet products, using prepolymers preferably containing blocked isocya-nate groups and the liquid polyamine/carbonic acid salt compositions as chain lengthening agents and/or cross-linking agents and at the same time as physiologically harmless blowing agents.

Description

$~ 7 .~10-241 Le~ 21,0 ~\ION-CRYST~LLI.`IE POLYA~I~IE /CAR30~1IC ~CI,;~
SAL. CO~IPOSITIO~IS, A PROCESS FOR T~EI~
PRE~PARATION AND THEIR USE ~OR THE ?RODUCTIO:`I
OF POLYURETHANE URE~S, ESPECIALL" FOA~ED COATI?iGS
.... .
B~C KGROUN~ OF THE INVENT ION
Field of the Invention This invention relates to new liquid or ,luid pol~amine/carbonic acid salt co~positions free from crystalline content and their preparation from mixtures containing at least one aliphatic or cycloalipn3tic polyamine, an aliphatic or cycloaliphatic hydroxyamine having at least one hydroxyl group and at least one amino group, and water, and optionally diluents and/or conventional auxiliary agents and additives, by mixing the aforesaid components with carbon dioxide. The invention fur-ther relates to the use o these liquid polyamine/carbonic acid salt compositions for the preparation of polyurethane ureas which are optionally foamed, especially for the coating of substrates or production of sheet products, using isocyanate prepolymers in which the isocyanate groups are prefer-ably blocked and the liquld polyamine/carbonic acid salt compositions as chain lengthening agents and/or crosslinked agents and at the same time as physiologi-cally harmless blowing agents.Descr ption of the Prior Art Xt is known to produce carbona-tes or bicarbon-ates of amines fro~ the said amines or polyamines, carbon dio~ide and water. The products obtained are generally fairly high ~elting, crystalline co~pounds which are insoluble or difficultly solu~le in the hydroxyl compounds conventionally used for the ~repara~
tion of polyurethanes. These crystalline carbonic acid Mo-2414 LeA 21,0~4 , salts of the amines, such as, for e~ample, bicar~onates and/or carbonates, optionally with different degrees oE
hydratlon, may be reacted Witll compounds con-taining isocyanate groups or compounds capable o reacting like 5 isocyanate groups to produce relatively high ~olecular weight compounds containing urea groups. Thus, US-~3,425,964 teaches the hardening of polyure-thane resins with solid aminecarbonates which have unlimited stabil-ity at 25C T~e said U.S. patent specification also 10 teaches the production of ,oamed products from the said compounds. JP-A 50,052,175 discloses the preparation of molded polyurethane products fro~ a polyurethane reaction ~ixture -~ith the addition of a (cyclo)-aliphatic diaminecarbonate such as, for example, 15 1,6-diaminoheYanecarbonate at temperatures below the decomposition temperature of the carbonate. To ilarden the product and fix the form, it is heated above the decomposition point of the amino carbonate.
DBP 838,217 describes the preparation of 20 linear polyureas by thermal condensation of diisocya-nates and carbonic acid salts of diamines. JP-A
7,213,068 teaches the use of aminecarbonates for t~e production of polyurethane foam heat sealing compounds.
In the present state of the art, amine/C02 25 adducts (carbamates or carbonates) are only known to be used in the form of crystalline products. These crystalline C02 adducts must be used ln a very finely divided form in order ,o avoid uneven hardening. In addition, it is necessary to take precautions to 30 prevent the deposition of such dispersed amine/C02 adducts. Furthermore, it is well ~nown to the man of the art that the cross-linking of compounds containing ~10-241~
Le~ l,Og4 ~ isocyanate groups with solid substances present in a heterogeneous ?hase can only be achieved with consider-able effort and frequently leads to inferior products since the said solid substances cannot be sufficiently 5 firmly linked and chemically incor?orated. ~he need to use the dia~ine/CO2 adducts in the form of very finely divided s-uspensions for their reaction with the polyisocyanates even applies to reactions of crystal-line CO2 adducts in highly polar solvents such as 10 dimethylfor~.amide (see DE-B 1,223,1~4).
In ~rench Patent No. 1,413,484 it has also been disclosed to prepare polyhydrazodicarboxylic acid amides or polyureas containing alcoholic hydroxyl groups in highly polar solvents such as dimethylforma-15 mide or dimethylacetamide by reacting solutions of thecarbonic acid salts of the diamines containing alcoholic hydroxyl groups, such as N-nydroxyethyl hexane~ diamine or 1,3-diamino-propanol-2 with aromatic diisocyanates in solvents at -20C to +30~C.
20 In this reaction, the carbonic acid salts are dissolved or suspended in highly polar solvents and are formed in the highly polar solvents, optionally with the addition of hydro~y~iamines and optionally also diamines or hydrazines not containing hydroxyl groups~ If, 25 however, diamines without hydroxyl groups (e.g., ethylene diamine) are added, insoluble, crystalline amine salts separate. Reaction of the amine salts with the polyisocyanates forms solu-tions from which hard, homogeneous polyureas are obtained by evaporation of 30 solvent.
It was, therefore, an object of the present invention to avoid the disadvantages known in the art ~o-2~1l ~e~ 21,084 ~99~ ~

of ~-sing crystalline aminemarbonates as chain leng-thening agents and enable aminesarbollate reactions to be carried out without highly polar solvents. It ~as also an object of the present intlention to provide 5 non-crystallins com~ositions containing c~rbonates and/or bicarbonates or alip'natic and/or cycloaliphatic primary or secondary polyamines, preLerably primary diamines. It -.~as also an object of the invention to provide higla proportions of cycloaliphatic primar~y 10 diamines in liquid form as an amine/carbonic ~cid salt mixture. I~ was yet a further object of the present invention to provide a process for ~he preparation of foamed sheet products rom polyurethane ureas, using physiologically harmless ?roducts as blowing agents.
15 ~he invention also seeks to provide an easily workable liquid non-crystalline mixture which will act bo-th as chain lengthening agent or cross-lin.'~ing agent and as blowing agerrt donor in the formation of polyurethanes, the carbon dioxide functioning as inert, physiologi-20 cally harmless blowing agent.
It has now surprisingly been found thatcarbonic acid salts (carbonates and/or bicarbonates) of mixtures of 1) aliphatic and/or cycloaliphatic polyamines, prefer-ably diamines ha~Jing ~rimary and/or secondary aminogroups and

2) hydroxy2mines to be defined in more detail below, preferably (poly)amines containing hydro~yalkyl groups, optionally in the presence of additional quantities of wa-ter and optlonally certain solvents as diluents ~1o-2~1 Le.~ 21,0~

do not crystallize but exist in a liquid or pasty 1uid state.
These carbonic acid salt nixtures are charac--terized by the absence of crystalline components. It 5 nas also surprisingly been found that solvents which are normally non-solvents for bicarbonates or carbon-ates may be added to the adduc-t mixtures before, during or after formation of the mixed carbonic acid salts according to the invention to lo~er the viscosity 10 without causing precipitation of the caxbonic acid salt compon.ents. Preferably, only a portion of the amino groups in -the mixture is converted into carbonic acid salts with carbon dioxide.
SUMMARY OF THE INVENT ION
The present invention relates to non-crystal-line, liquid or fluid polyamine/carbonic acid salt compositions of polyamines and CO2, characterized in tnat they contain 1) aliphatic or cycloaliphatic polyamines having primary and/or secondary amino groups (preferably ~rimary amino groups), preferably polyamines having 2 to 4 amino groups, most preferably primary diamines, especially cycloaliphatic diamines, and 2) aliphatic or cycloaliphatic hydroxypolyamines having at least one hydroxyl group and at least one amino group (preferably mono- to tris-hydroxyalkyl-polyamines, most preferably mono- and bis-hydroxy-alkyl-alkylene diamines)l components 1):2) being present irl proportions in the 3n range of from about 95:5 to 10:9G % by weight (-orefer-ably from about 30:20 to 25:75 % by weight, most prefer-ably from about ~5:35 to 30:70 ~ by weight), ;~o-2~
Le~ 21,084

3) opfionally diluents in the form of organic solvents having a boiling point b210w abou-t 160C
and being a~ least partially soluble in ~ater, in ~uantities of up to about 90~ by weight or cliluent (preferably up to about 60o by -~eight, mos-t prefar-ably up to about 30% by weight) in th~ total mixture of 1) to 6 ) /

4) optionally further known auxiliary agents and additives, 10 5) from about 0.31 mol to 5 mol (preferably from about 0.1 to 1.0 ~ol, most preferably from about 0.15 to 0.7 mol) of water per amine equivalent, but at least 1 mol of r~ater per mol o-f carbon dioxide, and i5 6) about 0.01 to 0.99 mol of CO2 per amine e~uiva-lent (preferably fro~ about 0.05 to 0.80 mol, most preferably from about 0.1 to 0.5 mol).
This invention also relates to a process for the preparation of non-crystalline, liquid or fluid 20 polyamine-carbonic acid salt compositions from poly amines and carbon dioxide, which comprises miYing 1) aliphatic or cycloaliphatic polyamines containing primary and/or secondary amino groups (preferably primary amino groups), preferably polyamines having from 2 to 4 amino groups, most preferahly primary diamines, especially primary cycloaliphatic diamines~ and 2) aliphatic or cycloaliphatic hydroxypolyamines having at least one hydroxyl group and at least one amino group (preferably mono- to tris-hydroxyalkyl-polyamirles, mos-t preferably mono- and di-hydroxy-alXyl-alXylene diamines) ~lo-2~1 Le~ 21,08 ~9~ ~'7 in proportions of 1):2) of from a~out 95:~ to 10:90 O
by weight (preferably from about 30:20 to 2~:75 ~ by weight, most preferably from abolit o5:35 to 30:70 ~ ~y weight)

5 optionally in the presence o.
3) diluents in the form of organic solvents which have a boiling point below about 160C (preferably below about 146C) and are at least partially soluble in water, in quantities of up to about 90 by weight of diluent (preferably fro~ about 0 to 60~ by weight, most preferably from about 0 to 30 by weight) in the total mixture of l) to 6), optionally adding 4) further `.cnown auxiliary agents and additives 15 and further mixing 5) water, the quantity of water being from about 0.01 to 5 mol (preferably from about 0.1 to 1.0 mol, most preferably from about 0.15 to 0~7 mol) of water 2er amine equivalent and at least 1 mol of -water per mol of carbon dioxide, and

6) sufficient carbon dioxide so that the quantity of incorporated CO2 per amine equivalent is from about 0.01 to 0.99 ~ol of CO2 (preferably from about 0.05 to 0.80 mol, most preferably from abou-t 0.1 to 0.5 mol)~
The invention also relates to the use of the non-crystalline polyamine/carbonic acid salt composi-tions for the preparation of polyurethane ureas which are optional:Ly foamed, preferably for the production of 30 optionally foamed coatings on textiles, non-~oven webs, leather-like or other substrates, from ~) isocyanate prepolymers containing an average of 2 to 4 optionally blocked aromatic and/or aliphatic Le.~ 21,~g4 ~ and/or cycloaliphatic isocyanate groups, having an isocyanate content of from about 1 to 24% ~y wei~ht (~rerera~ly ~rom about 1.7 to 6~ by weight), B) chain lengthening agents and/or cross-linking agents, and optionally C) known auxiliary agents and additlves and solvents, characterized in that component 3) comprises at least 50 equivalent percent (preferably at least 75~), most preLerably 100~ of the non-crystalline, liquid or fluid polyamine/carbonic acid salt compositions according to the invention with up to ;0 equivalent percent, if desired, of ccnventional chain lengthening agents or cross-lin'ring agents.
If desired, the polyamine/carbonic acid salt compositions may be restricted to smaller quantities, e.g. a~out 20-50 equivalent % used with about 80 to 50 equivalent ~ of conventional chain lengthening agents, but this is less advantageous.
DET~ILE~ DESCRIPTION OF THE INVEN~ION
The following co~pounds are examples of sl-itable polyamine components 1):
~inear or branch chained aliphatic diamines containing ~rlmary amino groups, e.g. 1,2-diaminoethane, 25 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diamino-butane, 1,5-diaminopentane, 1,6-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, l,ll-diaminounde-cane, 1,12-diaminododecane; or diamines containing 30 hetero atoms, such as 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxa-octane, 1,11-diamino-3,6,9-tri-oxa-undecane, 1,13-diamino-4,9-dioxa-tridecane, and 1,9-diamino-5-oxa-nonane.

Io 2~
Le~ 21,084 The following are pre~erred:
cvcloaliphaLic diamines having 2 primary amino groups, such as 5-amino-2,~,4-trimethyl-1-cyclo~entane-methyl-amine, 5 amino-1-aminomethyl-1,3,3-trime-thyl-cyclo-5 hexane (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohe~ane, 1,8-diamino-p-menthane, l-methyl-2,6-diaminocyclohexane, 1-methyl-2,4-diamino-cyclonexane, 4,4'-diamino-dicyclohexylmethane and its 2,4i- and 2,2'-isomers, 4,4'-diamino-3,3'-dimethyl-di-10 cycloh~xylmethane and its 2,4'- and 2,2'-diamino-isomers, ~,4'-diamino-dicyciohexylethane, 4,4'-diamino-dicyclohexylether, bis-~4'-aminocyclohexyl)-propane-(2,2), 4,4'-diamino-dicyclohexane~ 4,4'-diamino-3,3'-dl-ethyl-dicyclohe~ylme-thane, l,l-di-(4'-aminocyclohexyl) 15 cyclohexane/ 1,1-di-(4'-amino-3'-methylcyclohexyl)-cyclohexane, 4,4'-diamino-3,5-diethyl-3',5'-diisopropyl-dicyclohexylmethane, and 4,4'-diamino-3,3',5,5'-tetraethyl-dicyclohexyl~ethane in all the conformers and any mixtures of con~ormers of the cycloaliphatic 20 diamines.
Di- and polyamines containing tertiarv amino ~roups may also be used, e . g. bis-(3-aminopropyl)-methylamine, N,N'-bis-(2-aminoethyl)-piperazine and N,N'-bis-(3-aminopropyl)-piperazine.
Diamines having secondary amino groups may also be usecl although they are less pre~erred as sole components. Exa~les include N-methyl-ethylenediamine, N,N'-diethyl-ethylenediamine, N,N'-dibutyl-hexamethyl-enediamine, piperazine and 2,5-dimethyl-piperazine.
30 Hydrazlne, hydrazine hydrate and N,N'-diaminopiperazine are also suitable. Compounds havin~ 3 or 4 or even more primary and/or secondary amino groups may also be `vlo-241~
Le~ 21,084 g~7 used, e.~. 1,6,11-triaminoundecane, 1,5-dia~ino-3-~a-pentane, 1,8-diamlno-3,6-diaza-octane, 1,11-diamino-~ 3,6,9-triazaundecane, 1,14-diamino-3,6,9,12-tetraaza-te~radecane, 1,7-diamino-4-aza-heptane, 1,11-diamino-5 4,8-diaza-undecane, 1,13-diamin~-4,10-diaza-7-~ethyl-7-aza-tri-decane and 1,3,5-triamino-cyclohexane.
`~lonoamines such as methylamine, ethylamine, propylamine, isopropylamine, n-butylamlne, isobutyl-amine or tertiary-butylamine, cyclopentylamine, cyclo-10 hexylamine or piperidine or ~,N-dimethylhydra~ine may also be lsed in minor quantities (less than a~out 5 mol ~) in addition to the polyamines.
In the process according to the invention, it is preferred to use aliphatic diamines such as ethylene-15 diamine and 1,6-diaminohexane, and espeeially cycloall-phatie diami.nes sueh as 4,4'-diamino-3,3l-(C1-C~-alkyl)-dicyclohexylmethane compounds and 4,4'-diamino-3,3',5,5'-tetra-(C1-C4-alkyl)-dieyclohexylmethane compounds such as 4,4'-diamino-3,3l-dimethyl-dieyelo-20 hexylmethane, 4,4'-diamino-3,3'-diethyl-dicyclohexyl-methane, 4,4'-diamino-3,3',5,5'-tetraethyl-(or tetraiso-propyl)-dicyclohexylmethane, 4,4'-diamino-3,5-diethyl-3',S'-diisopropyl-dicyclohexylmethane and 5-amino-1-aminomethyl-:L,3,3-trimethyl-cyclohexane.
The aliphatlc or cycloaliphatic hydroxyamines used (Component 2) may oe compounds containing at least one primary, seeondary or tertiary hydroxyl group and at least one primary, secondary or tertiary amino group. Hydroxyamines having at least one hydroxyl 30 group and at least two primary and/or secondary amino groups are preferred. l~lono- to tris-hydroxyalkyl-poly-amines are pre~erably used, and particul~rly mono- and di-hydroxyalkyl-alkylenediamines.
Mo-2414 LeA 21,084 he ~ollowing are examples:
~lonoalkoxylated diamin.s derived from aliphatic straight chained or branched chained diamines, preferably with 2 to 12 carbon at~ms, or optionally al`xyl-substituted cycloali?hatic diamines OL- the cyclo-hexane, dicyclohe~yl, dicyclohexylmethane, dicyclohexyl~
2,2-propane and dicyclo'nexyl~ cyclohexane series and alkylene oxides such as ethylene oxide, propylene oxide, butylene-2,3-oxide or styrene oxide. ~o~oalkoxy-10 lated aliphatic diamines with 2 to 6 ~-atoms and in so~e cases cycloaliphatic dia~ines ~hicn have been alkoxylated with ethylene oxide or propylene oxide are pre'erred. The following are examples~ -hydroxy-ethyl)-ethylenediamine, ~ -hydroxyethyl)-~ropylene-15 1,2-diamine~ ~-(g-hydroxyethyl)-propane-1,3-dl.amine, -hydroxyethyl)-hexane-1,6-diamine, N-(g-hydroYy-ethyl)-.10decane-1,12-diamine, ~ hydroxypropyl)-etnylenediamine, ~-(g-hydroxypropyl)~ropylene-1,2-diamine, ~ -hydroxypropyl3-propane-1,3-diamine, 20 N-(~-hydroxypropyl~-butane-1,4-diamine, ~ -hydroxy-butyl)-ethylene diamlne, ~-(6-hydroxybutyl)-hexane-1,5-dia.~ine, N-(~-hydroxyethyl)-xylylene-1,3-diamine, .I-(3-hydroxyethyl)-cyclohexane-1,3- or 1,4-diamine, ~ -hydroxyethyl)-2,2,4-trimethyl-hexane-1,~-diamine, 25 1-methyl-2-amino-4-[`1-(2-hydroxyethyl)-amino]-cyclo-hexane, N-(~-hydroxyethyl)-isophoronediamine, and N-(~-hydroxyethyl)-4-aza~4-methyl-heptane-1,7-diamine.
~lso suitable are the bis-(hydroxyalkyl)-diamines obtained from the corresponding strai~ht chained or 30 branch chained aliphatic or cycloaliphatic diamines by alkoxylation with alkylene oxides, preferably with ethylene oxide and/or propylene oxide. F.xamples ~10-2414 .~ 21,0~4 ~9~

include N,~ DiS~ hydroxy~-thyl)-ethylenediamine, N~ bis-(3-hydroxypropvl)-ethylenediamine~ M~ ~bia~
(3-hydroxyethyl)-propylene-1,2-diamine, N,~'-bis-(~3-hydroxypropyl)-propane-1,3-diamine, N,l~'-bis-5 (~-hydroxyethyl)-1-methyl-2,4- or -2,6-diaminocyclo-hexane, ~,N'-bis-(~-hydroxypropyl)-l-methyl-2,6- or -2,4-diaminocyclohexane, ~,?~' bis-(~-hydroxyethyl)-isophoronediamine, N,N'-bia-(~-'nydroxypro2yl)-p-xylylene di~mine, and ~I-(g-hydroxyet}lyl)-N'-(~-hydroxy-10 propyl)-e-thylenediamine. ~lkoxylated tria~,ines and polyamines may also ~e used, e.g. tris-(~-hydroxyethyl)-1,6,11-triaminoundecane. ~i~tures o_ compounds at various stages of alkoxylation may also be used, e.g.
mixtures o- mono-, bis- and tris-hydroxvethyl-ethylene-15 diamine.
Compounds auch as 1,3-diamino-propanol-2, 1,6-diamino-hexanol-2, 1,5-diaminopentanol-3, 3,4-diamino-2,2-dimethylbutanol-1, the various diamino-cyclohexanols and l,ll-diaminoundecanol-~ may also be 20 used as hydroxyamines.
~ -~ydroxyethylhydrazine and ~-hydroxypropyl-hydrazine are suitable. The compounds and classes of compouncls mentioned above ~hich have two amino functions (primary, secondary or primary and secondary 25 amino ~3roups) are preferred since they react as diamines in the chain lengthening reaction with isocyanate compounds or i~aocyanate prepoly~ers (prefer-ably containing blocked isocyanate groups). .~mong t'nese components, C2-C6-al1-ylene diamines having 30 ~-hydroxyethyl and/or ~-hydroY~ypropyl groups are particularly preferred~ especially ~-hydroxyethyl- and ~-hydroxypropyl-mono- and -bis-ethylenediamines.

?10--241~
LeA 21,0~4 ~-hydroxyethyl-ethylenediamine is a particularly prefer-red compound.
Under certain conditions, monoamino-mono-hydroxyl or ~dihydroxyl compounds (containing primary or secondary amino groups) may also be used, e.g. 2-amino-ethanol, 2-methyl-2-aminoethanol, 2-ethyl-2-amino--ethanol, 6-methyl-3-oxa-6-aza-hexanol, and 6-hydroxy-hexylamine; also bis-hydroxyalkyl derivatives of primary amines, e.g bis-~-hydroxyethyl)-amine,~-hydroxyethyl)-oleylamine, bis-(~-hydroxypropyl)-amine, or N,N,N'-tris(~-hydroxypropyl~-ethylenediamine. Compounds such as 3-aminomethyl-3,5 J 5-trimethyl-cyclohexanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol and 2-amino-2-methyl-propanol may also be used.
These monoaminohydroxyl compounds are less preferred since in a reaction with isocyanate pre-polymers containing blocked isocyanate groups they react substantially with the amino group alone i.e. as mono-functional compounds. They should, therefore, only beused in minor quantities ~less than about 5% by weight) for these reactions since they function as chain breaking agents. However, when tlsed with isocyanate prepolynters which are not blocked, they behave as poly-functional compounds in their reactions with amino andhydroxyl groups.
Compounds containing one, preferably several hydroxyl groups and tertiary amino groups are also suitable as hydroxyamines. These include, for Mo-2414 LeA 21,084 ;7 -~:~99~

example, triethanolamine, tris-(~-hydroxypropyl)-amine, tetra-(B-hydroxyethyl)-ethylenediamine, tetra-(~-hydroxypropyl)-ethylenediamine, tetra-(~-hydroxyethyl)-isophorone diamine or di(C-hydroxyethyl)-methylamine, di~ hydroxyethyl)-butylamine or di(~-hyd nYvoropyl)-ethylamine or bis-(~-hydroxypropyl)-methyl3mine, -is-(~-hydroxypropyl)-hexylamine.
In their reaction with isocyanate compounds which are not blocked, these t-amino-polyols function 10 as polyol chain lengthening agents but they react too slowly with blocked isocyanate groups in isocyanate prepolymers at the usual reaction temperatures. In the latter case, they do not function as chain lengthening agents or cross-linking agents but as catalysts or 15 additives Suitable for use as diluent component 3) are organic solvents which are at least partially soluble in water and have a boiling point below about 160C, preferably below about 146 C. For example, there may 20 be used alcohols such as methanol, ethanol, n-propanol~
iso-propanol, n-butanol, sec.-butanol, tert.-butanol or isoamyl alcohol; ether glycols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
ether esters such as ethylene glycol-monomethyl ether 25 acetate and ethylene glycol-monoethyl ether acetate;
ethers such as tetrahydrofuran~dimethoxv-ethane or dioxane and esters such as ethyl formate, ethyl acetate and methyl propionate.
Ketones such as acetone, methyl ethyl ketone 30 and methyl isobutylketone are less preferred since they are liable to undergo reactions with the (primary) amines. Solvents containing amide, urea or sulphone sroups, such as dimethylformamide, di~ethylacetamide, Mo-241'1 LeA 21,0~4 methyl-pyrrolidone, -tetramethylurea or tecramethylen~-sulphone are not used or at the most may be added in quantities of up to about iO r~ by weight to the given solvents.
Suitable auxiliary agents and additives 4) include, for example, emulsifiers, antifoamin~ ayents, pigments, dyes, plasticizers, etc. and in general also the t~es of additives employed ~hen the compositions according to tne inventlon are used as cross-linking 10 co~ponents in heat hardening coating compositions, e.g.
stabilizers, dill~ents, substances to improve the flow properties, cell regulators, catalysts, reaction retarders, Elame retarding agents and other additives used in the usual quantities (see DE-A 2,854,38~, pages 15 25 to 32).
The process accordin~ to the invention for Qreparing the polyaminê/carbonic acid compositions is generally carried out by introducing a mixture of components 1) and 2) in proportions by weig~t in the 20 range of about 95:5 to 10:90 or in the preferred ratios already indicated above into a suitable vessel equipped with stirrer. Slight to moderate heating usually occurs when components 1) and 2) are brough-t together.
Tne addition of water may be carried out by 25 adding from abo-lt 0.01 to 5 mol of water ?er equivalent of basic nitrogell atoms (~referably from about 0.1 to 1.0 mol of water, most preferably from about 0.15 to 0.7 mol of water) to the mixture of components 1) and 2). ~lso possible although less preferred in practice 30 is the addition of the finished mi~ture of 1) and 2) to the given quantity of water or mixing of the quantity of water with one of the components 1) or 2),followed ~10-2~14 LeA 21,0~4 9~ ~'7 by addition oE tne other component. lhe water may also be mixed wit`n onlv a prol~ortion of 1) or 2) or of mixtures of 1) and 2) and the resultin~ rnixture ma~
su~sequently be combined witn the remaining quanti-ties 5 of 1) or 2) or of mixtures of 1) and 2). The addition of water in any of the variations indic~ted above is accompanied oy the evolution of heat. The carbon dioxide 5) may be added in the form of gaseous or solid carbon dioxide. Preferably, gaseous carbon dioxide is 10 introduced into or passed over a previously prepared mixr.ure o,~ 1), 2) and water (and optionally also diluent 3) and additives 4)). In the course of about Sminutes to 30 hours, preferably within a period of about 30 minutes to 6 hours, gaseous carbon dioxid is supplied 1~ in the quantity required to enable the mixture to ta~e up from about 0.01 to 0.39 mol, preferably from about 0.05 to 0.~ mol, most preferably from about 0.1 to 0.5 mol of carbon dioxide per amine equivalent. This is und~r the assumption tha-t the mixture of 1), 2) and 20 water land optionally further additives 3) and 4)) contains at least sufficient ~ater to ensure tha-t only salts of carbonic acid will form (c~rbonates or bicarbonates) and not salts of carbamic acid (carba-mates), i. 9 . that at least one mol of wa-ter is present 25 per mol of CO2 supplied. The amine mi~ture prerer ably continues to be gassed with carbon dioxide until saturation is reachedf i.e. until no furt'ner carbon dio~ide is taken up at any appreciable velocity. This saturation llmit is generally below ~he quanlity which 30 can theoretically be absorbed, hased on all the ~1 equi~alents present.

i~o-2414 LeA 21,034 ~9~ ~'7 The compositions obtained from polyamine 1), hyd~oxyami~e 2), -~a~er, carbon dioxide and, optionally additives, normally have a carbon dioxide content of from abo~lt 0.1 to 25~ by weight, preferably from abo~lt S 2 to lOg6 by -~,leight.
T'ne quantity o~ chemically ~ound carbon dioxide preisent may be demonstrated by removin~ a specified quantity of sam~le, subjecting it to a vacuum, optionally -~it`n simultaneous introduction of a 10 stream OL in~rt gas such as nitrogen, and adding acid, e.~. acetic acid, 'ormic acld, 'nydrochloric acid or sulphuric acid. The quantity by weight of chemically bound car~on dioxide may be calculated from the volume Oc carbon dioxide formed, ror example, by means of the 15 general gas equation. The C02 liberated may also be determined gravimetrically as 3aC03.
Components 3) and 4) may be added be~ore, during or after the reaction with carbon dioxide.
Component 3) is preferably added after the treatment 20 with carbon dioxide gas while component 4) is preferably added before this treatment. IE component 3) is added before the carbon dioxide, it may be added either to the mixture o 1) + 2) or to the mixture oF
1) ~ 2) ~ water or to the mixture of 1) ~ water or 2) 25 water.
Diluent component 3) nay be added, for example, with stirring at about 15 to 80C, preferably at about 25 to 60C. This may be carried out immediately or at an;~ time up to about 12 hours, prefer-30 ably about 30 minutes to 6 hours after the addition ofC2 has been ter~inated. It should be ointeil out again -that when used without component ~), t'nese diluents lead to the formation of crystalline carbonic i`lo-2414 Le~ 21,0 acicl salts. The quantity of component 3) based on t~e tot~l welght of the components is from about 0 to 90%
by weight, preferably up to about 60% by weight, rnost preferably up to about 30% by weight. Final adjustment of the mlxture of the polyamine/carbonic acid salt compositions may also be carried out by subsequently mixing.a ~olyamine/carbonic acid salt mixture with further polyamines, hydroxyamines, portions of water or mixtures of these components, optionally together with further diluent.
The polyamine/carbonic acid compositions prepared according to the invention and having the composition according to the invention may be used or the synthesis of polyurethane ureas, preferably by a reaction with isocyanate prepolymers based on excess quantities of polyisocyanates and relatively high molecular weight polyols and/or low molecular weight polyols and optionally further chain lengthening agent s .
The isocyanates used for the synthesis of the isocyanate prepolymers optionally containing blocked isocyanate groups (component A of the polyurethane starting mat.erials) are preferably aromatic but may also be aliphatic and/or cycloaliphatic polyisocya-nates, such as those described in some detail in US-A
3,984,607, 4,331,778 and 4,035 " 13, DE A 2,402,840, DE-B 2,457,387 and DE-A 2,854,384. The following are preferred according to the invention: 4 3 4'- and/or 2,4'-diisocyanatodiphenylmethane, the isomeric tolylene diisocyanates and their commercial mixtures or modifi-cation products, 3,3'-dimethyl-4,4'-diisocyana~odicyclo-Mo-2414 ~L~9~

hexylmethane, 4,4l-diisocyanatodicyclone~ylmethane, 1,5-hexanediisocyanate, isophorone diisocyanate and .~ixtures of these diisocyanates.
For the preparation of the isocyanate pre~oly-5 mers, these polyisocyanates may be reacted with rela-tively high molecular weight polyhydroxyl co~pounds containing from 2 to 8, preferably 2 or 3 hydroxyl groups and having a molecular weight of about 500 to 10,000, preferably from about 1000 to 6300, as also 10 described in detail in the above-mentioned publica-tions. ~ccording to the invention it is ~rererred to use propylene oxide polyethers having an average of 2 to 3 hydroxyl groups which may also contain polyethyl-ene oxide units and polyethylene oxide sequences as 15 well as hydroxypolyes-ters with melting points below about 60C which contain from 2 to 3 terminal end groups and have an average molecular weight OL from about 1000 to 6000. ~ixtures OL the above-mentioned hydroxy~olyethers with hydroxvpolyesters of adipic 20 acid, hexane-1,6-diol and neopentyl ~lycol having an average molecular weight of from about 1000 to 3000, esters based on hexanediol polyc.arbonates and mix-tures thereof with polyesters are preferred according -to the invention.
Low molecular weight polyols having a molecular weight of less than about 399, preferably less than about 300, of the kind known as chain lengthening agents, may also be used for -the ~repara-tion of the isocyanate prepolymers. According to the 30 invent.ion, the chain lengthening agents are ~referably used in a molar ratio to the relatively high ~olecular weight polyhydroxyl co~pounds of up to about lS:1, o-241~
Le.~ 21,084 1~9~ 7 prererably about 5:1. Preferred compounds include butane-1,4-cliol, trimethylolpropane, ~entaerythritol, nydroquinone-bis-hydroxyetnylethers and bis-(hydroxy-alkyl)-ether of 4,4'-bis-(h~droxxphenyl)-proparle.
5 Other suirable low molecular weight polyols ~ave been t~escribed in DE~ 2,854,384.
r.xcess polyisocyana-tes may also be r~acted with the low molecular -~eight polyols alone, e.~.
trimethylolpcopane may be reacted with excess diphenyl-10 methane-4,4'-diisocvanate to form an isocyanate ~repoly-mer having an isocyanate content of about 24~ hy weight. In -l.lese cases, however, the polyurethane forming reaction miYture preferably also contalns relatively high molecular weight polyols.
Preparation of the isocyanate prepoly~ers is carried out in known manner by reactlng the above-~entioned polyhydroxyl compounds with excess diisocyanates, preferably at about 70 to llO~C. The `~CO/OE~ ratio used is generally in the range of from 20 about 1.5:1 to 10:1, preferably fro~ about 1.7:1 tv 2.5:1. The weight proportion of isocyanate groups in the prepolymer is then in t'ne re~ion of about 1.0 to 24% ~CO, prererably from about 1.7 to 4.5% NCO.
The blocking agents used for the isocyanate 25 prepolymers may be phenols, tertiary alcohols, oximes, ~-dicarbonyl compounds, lacta~s, benzotriazoles et al.
These and other blocking agents have ~een described by Z. W. Wicks, Jr., Progress, in Org. Coatings _, 73-9g (1975); G. R. Griffin and L. J. ~illwe~tn in 30 Ind. Eng. Chem., Prod. ~es. and Develop. I, 265-268 (1962); A. ~amusis and K. C. Frisch in Film-Formin~
Co~ositions, Part I, I~arcel Dekker, l~ew York, 1967 and ;~o-2~
Le~ 21,084 S. '1~ Won~, ~. Damusis, ~ risch, R. L. Jacobs and J. ~ Long in J. ~lastO Plast. 11, 15-35 (1979).
Preferred blocklng asents are he-toximes of 'nydroxyl-amine and ketones such as acetone, methyl etilyl kQtone, 5 diethyl~etone, cyclohexanone, acetophenone and henzo-phenone. Methyl ecnyl ketoxi~e (butanone o-x1me) is particularly prelerred as blocking agent.
The blocked isoc~anate ~repoly~ers may be mi;~ed with organic solvents to adj US t them to the 10 optimum operating viscosity of Lrom about 20 to 40,000 mPas at 20~C~ the solvents bein~ ~re erably used in quantities of up to about 15~ by weight, most preferably up to about 10~ by weignt, based on the blocked isocyanate prepolymer. ~ince the isocyanate 15 groups are blocked, the solvents used need not neces-sarily be inert towards isocyanate groups. Examples of suitable solvents include isopropanol, ethylene glycol monomethyl ether ~nd ethylene ~lycol monoethyl ether and their ace-tic acid esters, methyl ethyl ketone, 2~ cyclohexanone, butyl acetate and dimethylformamide.
According to the invention, the composition containing polyamine /carbonic acid salts is used as cross-linking component a or the optionally blocked isocyanate prepolymers, as already lescribed above.
25 The polyamine 1) used within the composition is most preferably a 3,3'-dialkyl derivative of 4,4'-diamino-di-cyclohexylmethane, in particular 4,4'-diamino-3,31-di-me-'chyl-dicyclohexyl-methane. The compounds used as hydroxyamine 2) are preferably 2-hydroxyalkylamines 30 (2-hydroxyethyl- and 2-hydroxypropyl-amines) r with N-(~-hydroxyethyl)-ethylene diamine being particularly preferred. The blocked isocyanate prepolymers are ~1~-2414 Le~ 21,0 generally mixed ;~ith the polyamlne/carbonic acid salt cross-lin~ing composition in equal proportions of the equivalent weigilts of the components although less than complete cross-linking may be suitable ~or certain 5 purposes, in ~hicn case the equivalen-t ratio of (blocked) isocyanate groups to primary and/or secondary amino groups is generally, according to the invention, in the range of from about 1.35:1 to 0.95:1, preferably from about 1.25:1 -to 1:1. It sho~lld be emphasized 'nere 13 that for the reaction of ~he blocked isocyanate prepolymers, -the hydroxyl groups OL component 2) are not included in the calculation of equivalents since they generally do not react with the blocked isocyanate groups under the reaction conditions.
The chain leng-thening agent and/or cross-linking component B) preferably e~clusively contains the diamine/CO2 composition according to the inven-tion although up to about 50 equivalents percent of component B) may com~rise conventional chain lengthen-20 ing agents and/or cross-linking agents, e.g. aroma-tic di- and polyamines or hydra~ide co~pounds suc'n as 4,4'-diaminodiphenylmethane or 3,3',5,5'-tetraalkyl-4,4'-diaminodiphenylme-thane such as 3,3',5,5'-tetra~
ethyl-4,4'-diaminodipnenylmethane or 3,5-diethyl-3',5'-25 diisopropyl-4,4'-diaminodiphenylmethane. 3-ther suitable chain lenythening agents have been described, e.g. in D~-A 2,854,384.
Known additives such as catalysts, etc. may, of course, also be added in the usual quantities to the 30 reactive mixtures ready for use (lsocyanate prepolymers plus cross-lin~ing agents) or to their starting materials. Suitable compounds have been listed, for example, in DE-A 2,854~384.

ilo-2414 LeA 21,084 ~9~

Since carbon dioxide is liberated as blowing agent in the reaction of the polyamine/carbonic acid salt composition according to the invention to produce polyllrethane ureas, the polyurethane ureas obtained are 5 generally foamed ~roducts with a density generally amounting to about 25 to 90~ of that of the unroamed ~olyurethane compositions. Foaming may, if desired, he prevented or reduced by the application of pressure.
~hese reacti~e mixtures with their retarded reactivity 10 combined with the expanding or blowing reaction are, therefore, ~articularly suitable for direct and reversal coating on substrates su^h as ~loven and knitted fabrics, non-woven webs or natural or synthetic leather, at least one layer of the coating ~eing 15 produced as top coat, bonding coat and/or intermediate coat from the heat hardening reactive compositions described above. The build-up of the various layers may also be combined with the use of the usual one coat or two coat component polyurethanes known in the art.
The procedure generally entails first applying the top coat (preferably a paste of the reactive composition according to the invention or a conven-tional formulation) in ~ thickness correspondin~ to about ~0 to 80 g/m to an intermediate support, e.g.
25 a steel strip, a silicone matri~, a separating paper or the li.ke, drying it in a dryin~ channel, applying the bondin~ coat (optionally preceded by an intermediate coat) to the dried top coat in a thickness of about 30 to 100 g/m2, laminating the substrate thereto and 30 then heatin~ the coatin~ in another drying channel at about 120 to 190C, preferably about 140 to 170C for a few minutes and then remo~ing the coated substrate from i~o-241~
Le~ 21,084 ~9~4~

- 2~ -the separating support. ~he substra-tes used may b~
textile webs sucn as woven or knit-ted fabrics, non-woven webs or leather, split leather or leather fiber materials. When leather is used as substrate, S the drying temperatures employed for the bonding coat are about 60 to 110C, preferably about ~0 to 90C in order not to damage the leather substrate.
~s already mentioned above, the coating paste obtained from the compositions according to the 10 invention ~ay also be applied directly, e.~. to the textile substrate, by the direct s?read coating proses s .
The usual apparatus known in the art, such as roller appllcators, rubber cloth wipers, reverse roll 15 coaters, etc. are used for applying the reac-tive pastes by the transfer coating or the direct coating process.
For highly concentrated spread coating ~astes, the modern techniques of screen printing and engraved roller printing are also particularly advantageous.
~laterials coated with polyurethane ureas by the process according to the invention are suitable for the manufacture of shoe upper material and lining material, heavy duty work clothing, luggage material and the like, upholstery material and as substrates for 25 direct coated articles such as tarpaulins and conveyor ~el-ts, etc. and especially for clothing purposes. They have an exceptionally soft handle and advantageous folding and bending properiies.
The amine/carbonic acid salt composltions 30 according to the invention may, of course, also be reacted with isocyanate compounds in which the isocya-nate groups are not blocked. In this case, they are `10-2414 Le~ 21,084 added to th~ co~ponents containi~g compounds with isocya~ate reactive hydrogen atoms in quantities generally providing an equivalent ratio of NC0 to isocyanate rea~tive groups in the ~ange of from about 1.35:1 to 0.80:1, preferably of fro~
i.35:1 to 0.9'~:1.
For the p~oducti~n oF f~ams, ~or example, the mixture of polyamine/caJ~onic acid salt compositions with cata-lysts and optionally other auxiliary agents and diluents may be mixed with the isocyanate prepolymers, optionally in con-tinuously 3perating dosing and mixing apparatus.

EXAMPLES
Examples of Preparation ~uantities indicated in the following ~amples are parts by weight or percentages by weigh-t unless otherwise stated.
Example 1 800 g of 3,3'-dimethyl-4,4'-diamino-di_yclo-hexyl~ethane (3.36 ~ol), ~75 g of ~ -hydroxyethyl)-ethylene diamine (8.41 mol), 212 g of water (11.~ mol) and 1.3 1 of methanol are introduced into a reactlon vessel. While ~he reac~ion tempera-ture is maintained at 30 to 40,^ by external cooling with an ice bath, carbon dioxide is introduced until no further absorp-tion of C0~ is observed. r~hen methanol has been completely removed at 18 mbar/70C, the paste, which is thick at room temperature, is diluted at 20C with a mixture of ~490 g of 3,3'-diamino-4,4'-dimethyl-dicyclo-hexylmethane (10.46 mol), 1093 g of ~ hydroxyethyl)~
ethylenediamine (10.56 mol) and 133.6 g of water (7.42 mol)-mhe polyamine!carbonic acid salt composition, 'ilhich ia thiXotropic at room temperature and readily .~10-2~14 Le~ 21,084 fluid at 50nC, does not become thick a~ room temperature even after a storage time of over 6 months, shows no crystalline components and releases 1.5 1 of carbon dioxide from 50 g of the composition after the addition of excess 50% sulphuric acid.
Example 2 1178 g of 3,3'-dimethyl-4-4'-diamino-dicyclo-hexylmethane (4.95 mol)~ 705 g of N~(~-hydroxyethyl)-ethylene diamine (6.78 mol), 123 g of water (6.83 mol) and 200 g of glycol monoethyl ether are introduced into a reaction vessel. 77.1 1 (3.44 mol) of carbon dioxide are taken up within 20 minutes at a temperature rising from 40C to 62~. Immediately after the introduction of C2 has be~n terminated, the reactlon mixture is diluted with 385 g of glycol monoethyl ether. After the mixture has been left to stand for 40 minutes, it thickens to a paste. The thixotropic product mixture releases 1.4 1 of C02 from 50 g of mixture when excess 50% sulphuric acid is added.
Example 3 1178 g of 3,3'-dimethyl-4,4'-diamino-cyclo-hexylmethane (4.95 mol~, 705 g of N-~-hydroxyethyl)-ethylene diamine ~6.78 mol) and 123 g of water ~6.83 mol) are introduced into a reaction vessel. 76 1 (3.39 mol) of C02 are taken up within 20 minutes at a temp-erature rising ~rom 40C to ~2C. The mixture which has thickened to a paste ater one day is heated to 50C and diluted with 585 g of glycol monoethylether. 50 g of the total mixture yields 1.4 1 of carbon dioxide after the addition o excess 50% sulphuric acid. The product mixture prepared as described above is more fluid at every temperature than the products according to Examples 1 and 20 It does not thicken after 6 months Mo-2414 LeA 21,084 ~3~

storage, shows no crystalline deposits and is phase stable.
Example 4 1178 g of 3,3'-dimethyl-4,4'-diamino-dicyclo-hexylmethane (4.95 mol), 705 g of N (~-h~drox~Jethyl)-ethylene diamine (6.78 mol), 123 g of water (6,83 mol) and 199 g of glycol monoethylether are introduced into a reaction vessel. 76 1 (3.39 mol~ of carbon dioxide are taken up within 90 minutes. ~hen the mixture has been left to stand for 6 hours, it i5 diluted at 40C with 386 g of glycol monoethylether. The composition, which is stiff and thixotropic at room temperature and fluid at 50C, is a homogeneous monophasic mixture without crystalline components even after 6 months storage.
Example 5 326 g of a mixture of 80% of 1-methyl-2,4-di-aminocyclohexane and 20% of 1-methyl-2,6-diaminocyclo-hexane (2.55 mol), 163 g of N-~-hydro~yethyl~-ethylene-diamine (1.57 mol) and 63.g g ~3.55 mol) of water are introduced into a reactor. 34.6 1 (1.54 mol) of carbon dioxide are taken up within 45 minutes, the temperature rising to 75C in the process. The resulting reaction mixture is a clear solution having a viscosity at 20C
of 15,000 mPas. No rise in viscosity or separation of crystalline components or phase separatlon can be observed even after 6 months storage of the composition.
Example 6 258 g of isophorone diamine (1.52 mol), 214 g of diethanolamine (2.04 mol~ and 37.6 g of water (2.09 mol) are introduced into a reaction vessel and carbon dioxide is passed in. 24.9 1 of carbon dioxide (1.11 mol) are taken up in the course of one hour, during which the reaction temperature rises to 82C.
Mo-2414 LeA 21,084 .,~. .

7.

highly viscous, thixotropic paste without crystalline components is obtained on cooling.
Example 7 286 g of isophorone cliamine (1.68 mol), l91 g of triethanolamine (1.28 mol) and 41.8 g o-f water (2.32 mol) are introduced into a reaction vessel and carbon dioxide is passed in. 13.35 l of carbon dioxide (0.6 mol) are taken up within 45 minutes. A very highly viscous, thixotropic paste wi~hout any crystalline components is obtained on cooling.
Example 8 (Comparison Example)

8.1 Carbon dioxide is introduced into a solution of 50 g of isophorone diamine (0.29 mol), 5 g of water 15 (0.28 mol) and 150 ml of diethylether. A crystalline, colorless precipi~ate begins to form after a short tlme and its formation increases as carbon dioxide continues to be introduced. The precipitate is suction filtered !
washed with die~hylether and dried. It melts with 20 decomposition at 134 to 137~C.
8.2 Carbon dioxide is introduced into a solution of 50 g of a mixture of 80% or 1-methyl-?,4-diamino- and 20% of l-methyl-2,6-diamino cyclohexane (0.39 mol), 5 g 25 of water (0.28 mol) and 150 ml of methanol. A
crystalli.ne, colorless precipitate begins to form after a short time and its formation increases as carbon dioxide continues to be introdueed. This precipitate is suction filtered, Mo-2414 LeA 21,084 ......

3~ ~7 washed wlth diethylether and dried. It melts at 140 -to 143C with deco~position.
8.3 Carbon dioxide is introduced into a solution 5 of 50 g of 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane (0.2:L mol), 5 g of water (0.28 mol) and 150 ml of chloroben~ene. .~ crystalline, colorless precipitate begins to Lorm after a short time and its formation increases during further introduction of carbon 10 dioxide. This recipitate is suction filtered, washed with diethvlether and dried. It melts at 142 to 150C
with decomposition.
Example 9 500 g of 1,6,11-triamino-undecane (2.487 mol), ~5 ~15 g of a reaction product of ethylenediamine and propylene oxide in a molar ratio of 1:1 (0.43 ;~ol), 150 g of water (8.33 mol) and 2 1 of ethanol are introduced into a reaction vessel. Carbon dioxide is introduced at a reac-tion temperature of 30 to 40C maintained by 20 external cooling with an ice bath until the uptake of carbon dioxide has virtually ceased. ~Etex removal of the volatile constituents by distillation (at 70C/20 mbar) a transparent, highly viscous oil remains behind. A 50~ solution in isopropanol is clear, with a 25 viscosity of 39,000 mPas at 50C, and does not thicken until after 6 ~on-ths storage. 50 g of the isopropanol solution evolve 1.~ 1 of carbon dioxide after tAe addition of excess 50~ sulphuric acid.
Example 10 364 g of bis-(4-aminocyclohexyl) propane-(2,2) (1.5~ ~ol), 832 g of ~ hydroxyethyl)-ethylenediamine (8.00 mol) an~ 180 g (10 mol) of water are introduced ~10-2t14 Le.~ 21,084 ~3~

into a reaction vessel and gassed with carbon dioxide at a reaction temperature not exceeding 30C (external cooling). C~ continues to be introduced until l-t virtually ceases to be taken up. The initially low 5 viscosity composition thickens after one week to about 100,000 mPas/23C but shows no signs of crystalline components at this stage. 50 g of the carbonic acid composition evolve 7.4 l of carbon dioxide when excess 50% sulphuric acid is added.
10 Example 11 1178 g of bis-~3-methyl-4-a~inocyclohexyl)-methane (~.95 mol), 705 g of ~l-(B-hydroxyet~yl,-et~yl-enedia~ine ~ 6.78 mol), and 123 g of water (o.83 mol) are introduced into a reaction vessel. 76 l or CO2 15 (3.39 mol) are taken up witnin 20 minutes at a tempera-ture rising from 20C -to 6~C. Two hours after termina-tion of the introduction of CO2, the reaction mixture, l~hich is at that stage still a highly fluid reaction mixture, is diluted with 585 g of i-butanol.
20 50 g oE the whole mi~ture release 1.4 l of carbon dioxide after the addition of excess 50% sulphuric acid. The product mixture prepared as described is mor highly fluid at every temperature tllan the produc-ts according -to 2xamples 1, 2 and 3. It does no-t 25 thicken even arter 6 months s-tora~e, shows no formation of crystalline deposits and is phase stable.
~xample 12 345 g of 3,3',5,5'-tetraethyl-4,4'-diamino-di-cyclohexylmethane (1.07 mol), 113 g of a reaction 30 product of propylene diamine and ethylene oxide in a molar ratio of 1:1 (1 mol) and 56.6 g (3.14 mol) of water are introduced into a reaction vessel and treated Mo-24'.4 LeA 21,084 '7 with 62 g of carbon dioxide at 23 to 30C with external cooling until the rate of absorption of carbon dioxide has become very low. A clear carbonic acid salt composition of medium viscosity (19,000 mPas/23C) is 5 obtained. It shows no signs of thickening, deposition of crystalline components or phase separation after 6 montns storage. 50 g of the carbonic acid salt composi-tion evolve 4.0 1 of carbon dioxide af-ter the addition of excess 50% sulphuric acid.
10 Example 13 1997 g of 313'-dimethyl-4,~'-diamino-dicyclo-hexylmethane (8.39 mol), 1280 y oE a crude reaction product of ethylene diamine and ethylene oxide (molar ratio 1:1) containing ~.4~ water, 10.2~ ethylene-15 diamine, 51.4% of the monoethoxylation product, 12.3%of the diethoxylation product, and 19.6~ of the tri-ethoxylation product, and 127 g of water (7.06 mol) are introduced into a reaction vessel. 98.6 liters ( 4.40 mol) of carbon dioxide are taken up within 45 minutes 20 at a reaction temperature of 50 to 80C. After 3 hours, 950 g of isobutanol are stirred into the clear, low viscosity mixture. The product mixture, which is highly viscous at room temperature and readily fluid at 50C, does not thicken after half a year's storage, 25 shows no signs o crystalline deposits and evolves 1.5 l of carbon dioxide from S0 g after the addition of excess 50% sulphuric acid.

~lo-241~
LeA 21,084 Example 14 Comparison be~ween carbonate an~ carbarnate formation.
1) Carbonate of ethylenediamine (accordin~ -to the invention in the ~resence of water) 120 g of ethylenediamine (2 mol), 72 g of water (4 mol) and 500 ml of me-t~anol are in-troduced into a reaction vessel and treated ~lith carbon dioxide until saturation point at a reaction temperature o, at the most 30C with external cooling. The product crystalli~es shortly after the introduction of carbon dioxide is stopped. It is suction filtered, washed with 50 ~1 OL methanol and dried at 23C/20 mbar. 180 g of a colorless, erystalline product are ootained.
Melting ~oin-t: 161-165C (with deeomposltion).
Evolution of yas from 50 g of substanee a~ter -the addition OL excess 50% sulphuric acid: 11.85 1 of CO2 ~
Theoretieal evolution of gas from 50 g:
H2NCH2c~2NH2 CO2 10.77 1 (m.wt.: 104) 20 H2NCH2cH2N~2 2 CO2 15.1 1 (m.wt.: 148) ~2NCH2CH2NH2 H2o CO2 9.18 1 (m.wt.: 122) H2NcH2cH2NH2 H20 2 CO2 13.5 1 (m.wt.: 166) H2NCH2c~2NH2 2 H2O 2 CO2 12.17 1 (m.wt.: 184) ) *) most proba~le eomposition ~50-2414 LeA 21,084 Solubllit~ tests: (carbonate) Solvent 23C 80C ~eflllx Temperature Wa-ter (3~. 100C) ~+ ~ ~+
5 Dimethyl,ormamide (~p. 153C) - ~ ~
Dioxane (B~. 101C) - - -i-hutanol (3p. 108C) - no solubilit-~
~ moderate solubility ++ good solubility 2) Carbamate of ethylenediamine (without water) 120 g of et'nylenediamine t2 mol) (dehydrated over -~OH and distilled) are introduced into 500 ml of anhydrous methanol and gassed -~ith carbon dioxide until saturated. The methanol boils in spite of external cooling. The ~roduct crystallizec on cooling and is ,iltered off, washed with 50 ml of methanol and dried at 23C/20 ~bar. 174 g of a colorless, crystalline 20 product is obtained.
The mother liquor was not ~.~orked up. ~5elting point sintering from 100~C, decomposition Doint 160C.
Evolution of gas from 50 g of su'ostance on addition o~ excess 50Q sulphuric acid: found 10.6 1 of ;~5 CO2.
Theoretical evolution of gas from 50 g:
H2CH2CH2NH2 CO2 10.77 1 (m.wt.: 104) ) H2NCH2cH2NH2 2 C2 15.1 1 (m.wt.: 148) H2NCH2cH2N~2 H2CO2 9.18 1 (m.wt.: 122) 2 2 2 2 2 2 13.5 1 (m.wt.: 166) H2NCH2CH2NH2 2 H2O 2 CO2 12.17 1 (m.wt.: 184) *) most probable composition !lo-241~.
L~ 21,0g4 Solubillty tests (carbamate) ..
- Solvent 23C 100C Reflux Temperature Water + + +
5 Dimethyl L ormamide - ~+ t Dioxane - + ~~
i-butanol - ~+ ~+
Example 15 (Comparison car~onate/carbamate formation) 1) Carbonate (in the presence of water) 10 250 g of hexamethylenediamine (2.16 mol), 77.7 g of water (4.32 mol) and 500 ml of ~ethanol are intro-duced into a reaction vessel and carbon dioxide is passed through to saturation point (90 minutes) at a reastion temperature of maximally 30C (external cooling). Precipitation of carbonic acid salt begins shortly aft~r the onset of the reaction and intensicies durin~ the introduction of gas. The crystalline, color-less deposit is suction filtered, washed with 100 ml of methanol and dried at 23~C/20 mbar. 300 g of ?roduct are.obtained; mother liquor and wash water are not worked up. Melting point: 158-165C, evolutlon of gas from 50 g of substance on the addition of excess 50-sulphuric acid: found 8.14 1 of CO2.
Theoretical evolution oE gas from 50 g:
25H2NtCH2t6NH2 CO2 7.0 1 (m.wt.: 160) H2N~CH2t6~H2 2 CO2 10.98 1 (m.wt.: 204) H2N~CH2t6NH2 H20 CO2 6.29 1 (m.wt.: 178) H2NtCH2~6NH2 H2o 2 CO210.0 1 (m.wt.: 224) 2 ~CEI2~6NH2 2 H2O 2 CO2 8.42 1 (m.wt.: 266) ) *) most probable composi-tion `~So-2~14 L~ 21,084 Solubility tests (Carbonate) Solvent 23C 80C Reflux Temperature Water ++ -~+ ++
Dimethylformamlde -9ioxane i-butanol - + +
2) Carbamate (without water) 250 g of hexamethylenediamine (2.16 mol) and 500 g of methanol are introduced into a reaction vessel and gassed with carbon dioxide until saturation point is reached. The methanol begins to boil in spite of external cooling with an ice bath. The product does not begin to crystallize until it cools. It is suction filtered, t~ashed with 100 ml of methanol and dried at 23C/20 mbar. ~other liquor and washing solution are not worked up. 316 g of a colorless, crystalline product having a melting point o~ 1~3C preceded by sublimation or decomposition are obtained. 2volution of gas from 50 g of substance on the addl-tion of excess 50~ sulphuric acid: found 7.3 1 of CO2. When compar-ing this result with the theoretical evolution of gas from various compositions (see above), ~he most probable composition is found to be ~H2~CH2t6~H2 ' ~2 Solubility tests (carbamate) Solvent 23C 80C Reflux Temperature _ Water ~ + +
30 Dimethylformami~e + ++ ~+
Dioxane - + +
i-butanol - ++ ++

~1~-2414 Le~ 21,084 -3~-These examples show that the carbonic acicl adducts (carbona~es and carbamates) obta-lned by the reaction of carbon dioxide with ethylene diamine and 1,6-diamino~
heYane with or without the presence of water dlffer di-stlnctly from one another both analytically and intheir solubility properties.
EY~amples of practical applicatlo_ Example 16 Use of a coating composition according to the invention for producing an intermediate coat and a bonding coat a) Top coat of one~component polyurethane ~not according to the invention) A 25~ solution of a polycarbonate-polyester urethane in dimethylformamide having a viscosity of 10,000 mPas/25C is used to produce the top coat. It is prepared by solvent-free condensation of 1000 g (0.5 mol) of hexanediol polycarbonate, 1125 g (0.5 mol) of a butane-1,4-diol adipate, ~73 g (3.0 mol) of butane-1,4-diol and the equivalent quantity of 4,4'-diisocyanato-diphenylmethane. The solution of the aromatic one-compon~nt polyurethane in dimethylformamide is pigmented with 8% of a commercial pigment paste, Bayderm~ Schwarz-C-TO, available from BAYER AG, D-5090 Leverkusen. The pigmented top coat solution is appl:ied to a separating paper (wet application 120 g/m2) on a coating machine using~ an applicator roller wi-th doctor knife. The dime~hylformamide which evaporates during the passage through the first channel is taken to a recovery plant.
b) Intermediate coat (according to the invention) ~ t the second coating apparatus, a pot blown foam paste is applied as intermediate coat in a *Trademark Mo-2414 . -quan~ity of 160 g/m2. The foam paste compounded on the basis of blocked isocyanate prepoly~ers is crosslinked with a crosslinking mixture according to Exampl~ 1 and foamed up.
Composition of the pot foam paste:
An isocyanate prepolymer blocked w-ith butanone oxime is prepared from 2000 g (1.0 mol) of a polyether of propylene oxide, 1000 g (0.5 mol) of a polyester of hexane-1,6-diol/neopentyl glycol (mol proportion 65:35) 10 and adipic acid, 775 g (3.1 mol) of 4,4'-diisocyanato-diphenylmethane and 261 g (3.0 mol) of butanone oxide in 450 g of methyl glycol acetate, 89.5 parts of blocked isocyanate prepolymer, 0.5 parts of a silicone as foam stabilizer, Imprafix* 43053-fl~ssig available 15 from BAYER-AG D-5090 Leverkusen, 10 g of talcum, 5 g of pigment paste as described in a) and 7.3 g of a cross-linking mixture according to Example 1. The inter-mediate coat is placed in a second channel for foaming it and at the same time crosslinking it~ where it is 20 kept at 120-140~160C for a total dwell time of approx-imately 90 to 180 seconds and thus dried. The foam obtained as intermediate coat for building up the coating has a unit weigh~ of about 600 g/l.
c) Bonding coat (according to the invention) The paste of pot blown foam described above which is also used as intermediate coat is here used as bonding coat which is applied to the intermediate coat in a quantity of 60 g/m2, subjected to a preliminary reaction in a fir~ct passage through a channel at 135C
30 and then crosslinlced at 150 to 160~C after it has been lamillated ~o a cotton fabric.
~Trademark Mo--2414 Example 17 Use o~ a coating composition accordlng to the invention for the production of an intermediate coat and a bon i~
coat a) Top coat (not according to the invention) The top coat is prepared from a 90% high-solid-p~TR of a blocked isocyanate prepolymer having an isocyanate con~ent of 3.3~ prepared according to F,uropean Patent Appli--cation 13,890 where it is described as prepolymer B). The lO top coat paste consists of 1280 g of the blocked isocyanate prepolymer, 119 g of 3,3'-dimethyl-4,4'-diaminodicyclo-hexyl-methane, 140 g of a commercial pigment paste, as described in example 16a), 3 g of polydimethylsiloxane oil (Baysilone* OF-OH 502 available from BAYER-AG, ~ 5090 Leverkusen), and 30 g 15 of silicate filler, (Aerosil* 380 available from DEGUSS~, D-6000 Frankfurt). The coating pas-te (4000 mPas/20C) is applied to a separating paper in an amount of 70 g/m2 using a roller applicator with doctor knife and is hardened in a drying channel a~ 140 to 160C for 2 minutes.
20 b) Intermediate coat (according to the invention) 200 g/m2 of an intermediate coat consisting of pot blown foam paste are applied ~ith doctor knife in the second coa~ing apparatus. The foam paste compounded on the basis oE
the blocked isocyanate prepolymer described in Example 16 is 25 crosslinked with the crosslinking mixture according to Example 3 and spread coated.
Composition of the pot foam paste 89.5 parts of blocked isocyanate prepolymer having an isocyanate content of 3.0% prepared according to Example 16, 30 0.5 parts of silicone oil as described in example 16b) as foam stabilizer, 10 parts of talcum and 5 parts of plgment paste of example 16a) and 9.4 parts of the reac-tion mixture according to Example 2 as crosslinking agent and blowing agent.
'Trademark Mo-2414 The temperatures employed for the blowing and cross-linking reaction of the foam are as indicatsd in ~xample 15. The unit weight is 625 g/1.
c) Bondin~ coat (acsording -~o the invention) The pot blown foam paste described above ~which was also used for the intermediate coat is used here as bonding coat. The substance is worked up as described in ~xample 16.
~xample 18 Use of a coatin~ composition according to the invention ior the production of an intermediate coat and a bonding coat a) Top coat (not according to the invention) The top coat is produced from a pigmented 30 solution of an aliphatic one-component polyester urethane in toluene/isopropanol/ethylene glycol =
29:29:12 having a viscosity of 22,000 mPas/25C. The pol~lrethane is synthesized by the reaction of an isocyanate prepol~ner of 1700 g (1 mol) of a polyester prepared from hexane-1,6-diol, neopentyl glycol (65/35 mol ~) and adipic acid and 490 g (2.2 mol) of isophorone diisocyanate with 205 g (1.2 mol) of isophorone diamine in solution. The intermediate coat and bonding coat are ormed as in Example 16.
Example 19 Use of a blown foam paste according to tne invention as bonding coat _ _ a) Top coat ~not according to the invention) ~'he top coat is prepared from a 30% solution o a polyester urethane in dimethylformamide/methyl ethyl ketone ~1:1) having a viscosity of 30,000 mPas/25C. The polyester urethane consists o 1800 g Mo-2414 LeA 21,084 - '~o (2 mol) of a butane-1,4-diol adipate, 174 9 (1 mol) of tolylene diisocyanate, 186 9 (3 mol) of ethylene glycol and the equivalent quantity of 4,43-diisocyanatodiphenyl-methane (lO00 9). After the composition has been pigmen-ted (6 Do of the pigment paste of example 16a), it isapplied to a separating paper under known conditions to produce a top coat with a solid content of 30 g/m2.
b! Intermediate coat (not accoroing to the invention) 200 9/m2 of a pot blown foam paste of 1280 9 of 10 a blocked isocyanate prepolymer (preparation according to EP-A 13,890, see Prepolymer B), 119 9 of 3,3'-dimethyl-4,4'-diamino-dicyclohexlmethane, 20 9 of diphenyl-3,3'-disulphonic hydrazide, 3.0 9 of dimethylpolysiloxane as described in example 16b), and 70 9 of silicate filler, 15 as described in example 17a) are applied as intermediate coat by knife coating. The temperatures employed for the blowing and cross-linking reactions of the foam in its pas-sage through the channel (about 2 to 3 minutes) are 120-150-170 C. The cross-linked foam has a unit weight of 500 9/l.
20 c) Bondinq_coat (according to the in~ention) The bonding coat (60 g/m2) consists of a pot blown foam to which the textile substrate is laminated by the dry laminating process according to Example 16. The said foam has the following composition: 89.5 parts of blocked isocyana-25 te prepolymer prepared according to Example 16b), 0.5 parts ofa silicone, as described in example 16b), as foam stabilizer, 10 parts of talcum, 5 parts of pigment paste of example 16a), and 9.4 parts of a cross-linking mixture according to Example 4.
When the cross~linking mixture according to Example 4 30 is replaced by 9.4 9 of cross-linking mixture according to Example 11, the properties obtained were substantially similar.

Mo-2414 LeA 21,084 Examples 20,21 Use of a blown foam composition according to the invention as bondinq_coat The cross-linking mixture according to Example 4 used in Example 19c) was successfully replaced by 10.2 9 of cross-linking mixture prepared according to E~ample 9 and 7.3 9 of cross-linking mixture prepared according to Example 10.
Example 22 Use of a coating composition to the invention as bondin~
coat or intermediate coat a) Top coat (not according to the invention) The top coat is produced from a thickened, pig-mented 40O PUR dispersion in water. 1700 9 (1 mol) of a copolyester of hexane-1,6-diol, neopentyl glycol (65/35 molO) 20 and adipic acid are reacted with 303 9 (1.8 mol) of hexane-1,6-diisocyanate and 152 9 (0,8 mol) of the sodium salt of ethylene diamine-ethyl sulphonic acid as chain lengthening agent to produce the polyester urethane urea.
b) Bondinq coat (according to the invention) 80 9/m2 of pot blown foam paste according to Example l9c) in addition contair,ing 2.0 9 of highly dispersed silicate of example 17a) is used as bonding coat. The textile web is incorporated by lamination without preliminary reaction of the bonding coat which is subsequently reacted in its passage 3û through the channel at 120-150-170 C.

Mo-2414 LeA 21,084 L L~ >~

- 4~ -Example 23 ~se of a co~ting composition according to the lnvention as top coat and as bonding coat without intermediate coat The pot blown foam paste according to ~xample l~b) is applied with doctor lcnife to an lmpregnated separating ~aper to form on it a laye.r of 80 g/m2, and is cross-linked at 120-150-170C. The same coating paste ls then used to apply on this "foam top coat" a bonding coat in a thicXness corresponding to 50 g/m2, which is then laminated ~ith a textile substrate by the dry laminating process according to ~xample 16.
~xample 24 Pot blown foam paste havin~ the composition according to Example 16b) is applied by doctor knife coating to an impregnated separating paper to form thereon a layer of 100 g/m2, and this is then laminated with a textile we~ by the dry laminating process according to Example 16, Preliminary reaction: 135C, cross-linking reaction after laminating: 150-160C.
Example 25 a) Bonding coat (according to the invention) ~ polyester fabric weighing ca. 200 g~m2 is 25 primed with a pot blown foam paste which was used as bonding coat in Example l9c). Application: 70 g/m , cross-linking temperature in the channel: increasing 120 150-170C.
~) Top coat (not accordin~ to the invention) After priming, a compact high-solid-PUR layer is applied by knife coating in a tnicXness of 120 g/m . Cross-linXing: 120-150-170C. The coating ~o-2414 LeA 21,084 ~99 paste has the following composition: 1000 g of blocked isocyana~e prepolymer having an isocyanate content of 3.3~ prepared according to EP-A 13,~90, prepolymer B), 5.0 g of a silicone (Levacast* fluid S available ~rom BAYER-AG-5090 Leverkusen), and 10 g of a polyacrylate levelling agent (Acronal* 7002, available from BASF-AG, Ludwigshafen/~hein), 15 g of a commercial pigment paste o~ example 16a) and 90 g of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane as crosslinking agent.
lO Example 26 Use of a pot foam composition according to the invention as intermediate coating paste a) Top coat (not according to the invention) The polyurethane solution described in Example 15 16a) is used to produce a top coat film with a solid content of 30 g/m2 on a separating paper.
b) Intermediate coat (according to the invention) . . _ 200 g/m2 of a pot blown foam paste is applied as intermediate coat to the a~oresaid top coat by 20 doctor knife coating. Composition o~ foam paste: 89.5 parts of blocked isocyanate prepolymer as descr~bed in Example 16b) having an isocyanate content of 3.0%, 0.5 parts of silicone as foam stabilizer, as in example 16b), 10 parts of talcum and 5 parts of pigment paste, 25 as in example 16a), 9.4 parts of reaction mixture according to Example 12 as crosslinking agent and blowing agent.
Temperatures employed for blowing and cross-linking the foam: 120-140-160~C, dwell time in the 30 channel: 90 seconds.
7.7 o:E crosslinking blowing agent according to Example 13 was used instead o~ 9.4 g crosslinking blowing agent according to Example 12. The unit weights are about 650 g/l.
35 *Trademark Mo-2414 c) sond ng coat (not according to the inventi~n) The bonding coat used is a 3~ polyurethane solution in dimethyllormamide/methyl ethyl ketone/
toluene (30:30:40), tha polyurethane consisting of 2000 g o' a polyester of polypropylene o~ide, 780 g of diiso-cyanatodiphenylmethane and 108 g of butane-1,4-diol.
The bonding coat is applied with a ~let applica-tion of about 120 g/m2 to the foamed intermediate coat by doctor knife coating. ?ieces of split leather are placed with light pressure onto the wet bonding coat and the solvent mi~ture is evaporated oy circula-t-ing air at 80 to 30C. The dressed split leather hasan excellent grain and nandle.
Examples of ~ractical application with isocyanate prepoly~ers which are not blocked Example 27 0.3 ~arts of dibutyl tin dilaurate and 0.6 parts of diazabicycloundecane are dissolved in ~ parts of tne product from Example 7 (OH number 1245). This 20 mixture is added to 115 parts of an isocyanate prepoly-mer which has an isocyanatecOntent of 4~ and has been prepared from isophorone diisocyanate and a polypropyl-ene glycol having an average molar mass oE ~000. The mi~ture is vigorously stirred for 30 seconds with a 25 high speed stirrer (index 100, i.e. equivalen-t quanti-ties o~ NCOtchain lengthening agent).
The freely expanded foa~ `nas a cream ti~e of about 60 saconds and is nardened by 10 minutes temper-ing at ~0CO The foam, which has little elasticity, 30 has a uniform pore structure and good tear pro~agation resistance.

~lo-2414 LeA 21,0~4 ~9~

_ ~5 -Example 28 0.3 ~arts of dibutyl tin dilaurate and 0.~
parts of dia~abicycloulldecene are dissolved in 5 parts of the product from ~xample 13 IO~ number 1052) obtained befor2 mlxing with isobutanol. ~he resulting mixture is added to 38 ~arts of thP above-mentioned isocyanate prepolymer and vigorouslv mlxed for 50 sesonds, uslng a high speed stirrer a-t room tempera-ture. The freely expanded foam has a cream time of 75 seconds an~ is hardened for 10 minutes at 80C. The soft '~oam has no residual tac'~iness and it 'nas satisfac-tory elasticity and very good tear propagation resist-ance.
~ lthough the invention has been described in detail in -the foregoing for the purpose of illustra-tion, it is to be understood that such detail is solely for that pur~ose and that variations can be made therein by those skilled in the art ~ithout departing from the spirit and scope of the invention exce t as it may be limited by the claims.

'.~lo~~414 LeA 21,084

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Non-crystalline, liquid or fluid poly-amine/carbonic acid salt compositions from polyamines and CO2, which are prepared by mixing 1) aliphatic or cycloaliphatic polyamines having primary and/or secondary amino groups, 2) aliphatic or cycloaliphatic hydroxyamines having at least one hydroxyl group and at least one amino group in quantitative proportions of 1) to 2) of from about 95:5 to 10:90 % by weight, optionally 3) diluents in the form of organic solvents having a boiling point below about 160°C and at least partial solubility in water, in quantities of up to about 90% of solvent in the total mixture of 1) to 6), and optionally 4) auxiliary agents and additives with 5) from about 0.01 mol to 5 mol of water per amine equivalent, wherein the quantity of water must be at least 1 mol of water per mol of CO2, and subsequently 6) adding sufficient CO2 to incorporate from about 0.01 to 0.99 mol of CO2 per amine equivalent.

2. The polyamine/carbonic acid salt composi-tions according to Claim 1, characterized in that they contain aliphatic or cycloaliphatic polyamines having from 2 to 4 primary amino groups.

3. The compositions according to Claim 2, characterized in that they contain mono- to tris-hydroxyalkylpolyamines as hydroxyamines 2).

4. The compositions according to Claim 2 or 3, characterized in that the compositions contain the polyamines 1) and hydroxyamines 2) in proportions in the range of from about 80:20 to 25:75 % by weight.

5. The compositions according to Claim 2 or 3 which comprise using from about 0.1 to 1.0 mol of water per amine equivalent.

6. The compositions according to Claim 2 or 3 which comprise adding sufficient CO2 to incorporate from about 0.05 to 0.8 mol of CO2 per amine equivalent.

7. A process for the preparation of non-crystalline, liquid or fluid polyamine/carbonic acid salt compositions from polyamines and CO2 which comprises mixing 1) aliphatic or cycloaliphatic polyamines having primary and/or secondary amino groups, 2) aliphatic or cycloaliphatic hydroxyamines having at least one hydroxyl group and at least one amino group in proportions of 1) to 2) of from about 95:5 to 10:90 % by weight, optionally 3) diluents in the form of organic solvents having a boiling point below about 160°C and at least partial solubility in water, used in quantities of up to about 90% by weight of solvent in the total mixture of 1) to 6) and optionally 4) auxiliary agents and additives with 5) from about 0.01 to 5 mol of water per amine equivalent, the quantity of water being at least 1 mol of water per mol of CO2, and subsequently 6) adding sufficient CO2 to incorporate from about 0.01 to 0.99 mol of CO2 per amine equivalent.

8. The process according to Claim 7 wherein primary diamines are used as component 1) and mono- and di-(.beta.-hydroxyalkyl)-alkylene diamines are used as component 2).

9. The process of Claim 7 or 8 which comprises mixing components 1) and 2) and optional components 3) and 4) with 5) from about 0.1 to 1.0 mol of water per amine equivalent, and subsequently 6) adding sufficient CO2 to incorporate from about 0.1 to 0.5 mol of CO2 per amine equivalent.

10. Polyurethane ureas which are optionally foamed and prepared from a reaction mixture comprising A) isocyanate prepolymers with an isocya-nate content of about 1 to 24% by weight having an average of from 2 to 4, optionally blocked, aromatic and/or aliphatic and/or cycloaliphatic isocyanate groups and B) chain lengthening agents and/or cross-linking agents comprising at least 50 equivalent percent of the non-crystalline polyamine/carbonic acid salt compositions of Claim 1.

11. Polyurethane ureas which are optionally foamed and prepared from a reaction mixture comprising A) isocyanate prepolymers with an isocya-nate content of about 1 to 24% by weight having an average of from 2 to 4, optionally blocked, aromatic and/or aliphatic and/or cycloaliphatic isocyanate groups and B) chain lengthening agents and/or cross-linking agents comprising at least 50 equivalent percent of the non-crystalline polyamine/carbonic acid salt compositions of Claim 2.

12. Polyurethane ureas which are optionally foamed and prepared from a reaction mixture comprising A) isocyanate prepolymers with an isocya-nate content of about 1 to 24% by weight having an average of from 2 to 4, optionally blocked, aromatic and/or aliphatic and/or cycloaliphatic isocyanate groups and B) chain lengthening agents and/or cross-linking agents comprising at least 50 equivalent percent of the non-crystalline polyamine/carbonic acid salt compositions of Claim 3.

13. The polyurethane ureas of Claims 10, 11 or 12 wherein the isocyanate groups of component A) are blocked with blocking agents for isocyanate groups and component B) comprises 100 equivalent percent of said non-crystalline polyamine/carbonic acid salt composi-tions.